CN115678591A - Method for removing mercaptan from light naphtha - Google Patents

Method for removing mercaptan from light naphtha Download PDF

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CN115678591A
CN115678591A CN202110870183.2A CN202110870183A CN115678591A CN 115678591 A CN115678591 A CN 115678591A CN 202110870183 A CN202110870183 A CN 202110870183A CN 115678591 A CN115678591 A CN 115678591A
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manganese
molecular sieve
light naphtha
temperature
manganese oxide
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晋超
张秋平
褚阳
孔令江
翟维明
刘锋
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

The invention discloses a method for removing mercaptan from light naphtha, which comprises the step of contacting a manganese oxide molecular sieve with a light naphtha raw material containing mercaptan at the temperature of between normal temperature and 200 ℃. The method can remove sulfur-containing substances in the light naphtha at normal pressure, normal temperature or lower temperature, and the sulfur-containing substances are purified by utilizing the special crystal structure of the molecular sieve through a mode of combining adsorption with catalytic conversion to obtain the light naphtha with ultralow sulfur content. The manganese oxide molecular sieve used in the invention has the advantages of low cost, high desulfurization precision, high sulfur capacity, high single-pass conversion rate, convenient operation of the production method, simple process and contribution to industrial popularization.

Description

Method for removing mercaptan from light naphtha
Technical Field
The invention relates to a clean treatment method of industrial oil products, in particular to a method for removing mercaptan from a light naphtha component.
Background
With the rapid development of the petrochemical industry in China, the production capacity of ethylene is improved year by year, so that the by-product cracked carbon five-carbon six-fraction of an ethylene device is continuously increased, and the comprehensive utilization project of light naphtha in China is driven to be vigorous. In particular, the sulfur content of light naphtha fractions tends to increase gradually due to the effect of the heavy petroleum feedstocks. The isomerization process of the light naphtha fraction uses a noble metal catalyst which is particularly sensitive to sulfur, the sulfur element can make the catalyst lose activity, the service life and the effect of the catalyst are influenced, the desulfurization technology becomes an effective measure for the comprehensive utilization of the catalyst, and the production of clean light naphtha fraction creates good and high-quality raw materials for downstream utilization. Among sulfides, mercaptan is an important sulfide, and its presence not only causes the generation of offensive odor but also degrades the quality and stability of the oil, because mercaptan is an oxidation initiator, which causes the oxidative polymerization of unstable compounds in the oil to form a colloidal substance. Mercaptans are also corrosive and can also initiate corrosion of elemental sulfur. Therefore, in the production of petroleum products, mercaptans in the oil must be removed. In addition, light naphtha isomerization processes require that the sulfur content in the distillate be reduced to below 0.1 μ g/g, which places more stringent requirements on the mercaptan sulfur content.
Chinese patent CN1482210A provides a catalytic cracking gasoline adsorption refining technology, which utilizes two adsorbents to remove the polarity of sulfide in catalytic cracking gasoline. The method comprises the steps of taking a mixture of alumina, ferric oxide and a molecular sieve as a carrier, taking an impregnated metal as an active phase, selectively adsorbing mercaptan sulfur in gasoline, and after selective deep desulfurization, wherein the content of the mercaptan sulfur in the gasoline is less than 10 mu g/g, and the total sulfur content is less than 300 mu g/g. CN200410010353.6 heats the poor gasoline to 20-220 ℃ at a volume space velocity of 0.1-10h -1 And the sulfur content of the desulfurized gasoline is reduced from 1290ppm to 800-400ppm, and the sulfur content of mercaptan is reduced to below 10 ppm.
The analysis shows that the adsorption desulfurization technology can remove the mercaptan sulfur content of gasoline to below 10ppm, but still cannot meet the requirement that the sulfur content of light naphtha components is less than 0.1ppm, so that the development of a method for removing mercaptan from the light naphtha components at low temperature with high precision, high sulfur capacity and low cost has very important significance.
Disclosure of Invention
The invention aims to provide a method for removing sulfur content in light naphtha to meet the requirements of a light naphtha isomerization process. In order to achieve the above object, the present invention specifically includes the following:
the invention provides a method for removing mercaptan from light naphtha, which comprises the step of contacting a manganese oxide molecular sieve with a mercaptan-containing light naphtha raw material at the normal temperature to 200 ℃.
The method can remove sulfur-containing substances in the light naphtha at normal pressure, normal temperature or lower temperature, and the sulfur-containing substances are purified by utilizing the special crystal structure of the molecular sieve through a mode of combining adsorption with catalytic conversion to obtain the light naphtha with ultralow sulfur content. The manganese oxide molecular sieve used in the invention has the advantages of low cost, high desulfurization precision, high sulfur capacity, high single-pass conversion rate, convenient operation of the production method, simple process and contribution to industrial popularization.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The sulfur content of the invention generally adopts the mass content calculated by sulfur element, generally adopts mass percentage or ppm as a measurement unit, and the light naphtha treated by the method of the invention is lower than 0.1ppm, thereby meeting the requirements of subsequent processes on the sulfur content.
The invention provides a method for removing mercaptan from light naphtha, which comprises the step of contacting a manganese oxide molecular sieve with a light naphtha raw material containing mercaptan at the temperature of between normal temperature and 200 ℃.
According to the invention, the contact conditions are conventional desulfurization conditions or milder than conventional conditions, such as normal pressure, normal temperature to 150 ℃, and the mass ratio of the manganese oxide molecular sieve to the light naphtha raw material containing mercaptan is 1-200. The normal temperature of the invention refers to the environmental temperature which does not need to be heated, and is generally 13-35 ℃, that is, the temperature range of the contact condition of the invention can be 15-200 ℃, 20-200 ℃ and the like according to the difference of the environmental temperature.
In the present invention, the source of the sulfur-containing light naphtha, the kind and content of the mercaptan are not particularly limited, and the mercaptan compound is, for example, one or more selected from the group consisting of methyl mercaptan, ethyl mercaptan, propyl mercaptan, n-butyl mercaptan, 3-methyl-1-butyl mercaptan and hexyl mercaptan. In some embodiments, the thiol compound to manganese oxide molecular sieve mass ratio is from 0.1 to 50:1.
the place where the desulfurization adsorbent is contacted with the sulfur-containing light naphtha feedstock according to the present invention is not particularly limited, and may be various types of reactors well known to those skilled in the art, preferably a fixed bed reactor, so that the sulfur-containing light naphtha feedstock is continuously passed through and rapidly separated. In the contact process, the contact efficiency can be increased by various conventional modes, and the mercaptan removal effect is improved.
The manganese oxide molecular sieve can be selected from one or more of birnessite, bussel ore, birnessite, barium manganite, potassium manganite and manganosite.
The specific surface area and pore volume of the manganese oxide molecular sieve of the present invention are not particularly limited, and generally, the specific surface area may be 50 to 300m 2 Per g, pore volume can be 0.2-1.2cm 3 /g。
The source of the manganese oxide molecular sieve is not particularly limited, the manganese oxide molecular sieve can be a commercial reagent, and can also be prepared by the raw materials, so long as the composition and the content meet the corresponding requirements of the invention. In order to better implement the method of the invention, the invention provides a method for preparing the manganese oxide molecular sieve, which is specifically described as follows:
(1) Carrying out hydrothermal synthesis reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound; (2) And collecting the solid product, washing, drying and roasting to obtain the manganese oxide molecular sieve.
Wherein, the manganese compound in an oxidized state and the manganese compound in a reduced state are relative; the manganese compound in an oxidized state is generally referred to as containing a relatively high valence state of manganese (e.g., mn) 7+ 、Mn 6+ Etc.), reduced manganese compounds generally refer to compounds containing relatively low levels of manganese (e.g., mn) 2+ Etc.). For example, the oxidized manganese compound is selected from one or more of potassium permanganate, potassium manganate and sodium permanganate, and the reduced manganese compound is selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride; preferably, the molar ratio of the oxidized manganese compound to the reduced manganese compound is (0.2 to 3): 1.
the hydrothermal reaction in step (1) is carried out under the conventional conditions in the field, for example, the temperature of the hydrothermal synthesis reaction is 60-200 ℃, preferably 80-150 ℃, and the reaction time is 1-36 h, preferably 2-24h.
Washing the precipitate obtained in step (1) as required, wherein washing refers to washing the collected solid product with deionized water until the washing solution is neutral (for example, pH 6.5 to 7.5).
The drying and calcination in the step (2) are conventional operations in the art, and the relevant conditions are not particularly limited, for example, the temperature of the drying in the step (a-3) is 80 to 350 ℃, preferably 100 to 300 ℃, and the time is 1 to 24 hours, preferably 2 to 12 hours; the roasting temperature is 200-900 ℃, preferably 250-800 ℃ and the time is 0.5-12 h, preferably 2-6 h. The calcination may be carried out in an air atmosphere or in an inert gas atmosphere, preferably N 2 The reaction is carried out in an atmosphere. Through the steps, the manganese oxide molecular sieve can be prepared.
In order to further improve the performance of the desulfurization adsorbent, before the hydrothermal reaction in the step (1), the operation of adding acid into the aqueous solution is included, and the pH value of the aqueous solution is adjusted to 0.2-3; the acid may be common inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, etc., or organic acid such as acetic acid, etc. for achieving the above purpose.
The method provided by the invention can directly obtain light naphtha with ultralow mercaptan content at a lower temperature, the manganese oxide molecular sieve has the advantages of low cost, high desulfurization precision, high sulfur capacity, high conversion per pass, convenient process of the mercaptan removal method, simple operation and contribution to industrial popularization.
The present invention is further illustrated by the following specific examples, which describe preferred embodiments, but which are not to be construed as limiting the invention, and any person skilled in the art may, by applying the above teachings, modify the equivalent embodiments equally.
Reagents, instruments and tests
Unless otherwise specified, all reagents used in the invention are analytically pure, and all reagents are commercially available.
The model of the XRD diffractometer adopted by the invention is an XRD-6000X-ray powder diffractometer (Shimadzu Japan), and the XRD test conditions are as follows: cu target, K α ray (wavelength λ =0.154 nm), tube voltage 40kV, tube current 200mA, scanning speed 10 ° (2 θ)/min.
H used in the invention 2 The S analyzer was a German SICK GMS810 hydrogen sulfide analyzer.
Preparation example 1
Dissolving 3.17g of potassium permanganate in 40.55g of deionized water, heating and stirring to dissolve the potassium permanganate to form a potassium permanganate solution, mixing the potassium permanganate solution with 5.78g of 50 wt% manganese sulfate solution, adding 6ml of nitric acid to adjust the pH value of the solution to 1.0, stirring uniformly, and reacting for 24 hours at 130 ℃.
The resulting brown precipitate was filtered and washed several times with deionized water until the pH of the washings =7, then the solid product was dried at 120 ℃ overnight, followed by calcination at 400 ℃ for 4h in an air atmosphere to produce manganese oxide molecular sieve A1: OMS-2-Hydro.
Preparation example 2
According to the feeding of preparation example 1, a potassium permanganate solution, a manganese sulfate solution and nitric acid are mixed and then transferred to a flask provided with a condenser tube to react for 24 hours at 120 ℃, and other steps are the same as the preparation example 1, so that a manganese oxide molecular sieve A2 is prepared: OMS-2-Ref.
Preparation example 3
The same procedure as in preparation example 1 was carried out, except that the calcination temperature was different, and calcination was carried out at 750 ℃ for 4 hours in an air atmosphere to obtain a manganese oxide molecular sieve A3: OMS-2-Hydro-750.
Preparation example 4
The preparation of a manganese oxide molecular sieve was performed in the same manner as in preparation example 1, except that the solid after the hydrothermal reaction was not calcined to prepare a manganese oxide molecular sieve A4: OMS-2-Hydro-750-No.
Preparation example 5
250ml of 5.5mol/L NaOH solution and 0.5mol/L MnCl 2 200ml of the solution was rapidly mixed, oxygen was introduced into the mixed solution at a flow rate of 50L/h, and the solution was stirred continuously.
After 4 hours of reaction, the reaction solution is filtered by deionized water until the pH value of the solution is 7.0-7.5, the solution is dried at 120 ℃, and then the solution is roasted for 4 hours in the air atmosphere of 400 ℃ to obtain the manganese oxide molecular sieve A5, namely the manganese oxide delta-MnO 2 (also known as birnessite).
Preparation example 6
250ml of 5.5mol/L NaOH solution and 0.5mol/L MnCl 2 200ml of the solution was rapidly mixed, oxygen was introduced into the mixed solution at a flow rate of 50L/h, and the solution was stirred continuously.
After 4 hours of reaction, the reaction solution was filtered with deionized water until the pH of the solution was 7.0-7.5 to obtain a mixture, which was dispersed in 500ml of 1mol/L MgCl 2 Stirring the solution for 12h, reacting at 100 ℃ for 6h, washing, filtering, drying at 120 ℃, and roasting at 400 ℃ in the air atmosphere for 4h to obtain the manganese oxide molecular sieve A6, namely the manganese oxide molecular sieve OMS-1.
Comparative example 1
The existing commercial light naphtha sweetening catalyst zinc oxide + copper oxide is selected to form (according to the mass 1:1) manganese oxide D1.
XRD analysis is carried out on the manganese oxides obtained in the preparation examples and the preparation comparative examples, A1-A4 all show characteristic peaks of OMS-2, which indicate that the manganese oxides have an OMS-2 molecular sieve structure, A5-A6 show characteristic peaks of OMS-1, which indicate that the manganese oxides have an OMS-1 molecular sieve structure; d1 did not show characteristic peaks for OMS-1 and OMS-2.
Examples
The manganese oxides of preparation examples 1 to 6 and comparative example 1 were evaluated for their effect on mercaptan removal, and the reaction processes were as follows: adding 20ml of oil into a reaction bottle, adding different types of mercaptan into the reaction bottle, stirring uniformly, adding 0.2g of manganese oxide, heating and stirring, and filtering the manganese oxide after the reaction is finished to obtain a liquid-phase product (wherein example 1 is an industrial oil product, and no mercaptan is required to be added additionally)
Example 1
Adding 20ml of industrial light naphtha mixed oil into a reaction bottle, wherein the content of thiol in the industrial light naphtha is 1.0ppm (calculated by the mass of sulfur elements, including methyl mercaptan, ethyl mercaptan and propyl mercaptan), adding the industrial light naphtha into the reaction bottle, uniformly stirring, adding 0.2g of manganese oxide A1, stirring and reacting for 3 hours at room temperature and normal pressure, filtering the manganese oxide after the reaction is finished, namely an obtained liquid product, and calculating the concentration of the methyl mercaptan in the liquid product after the adsorption reaction by using gas chromatography.
Example 2
The adsorptive conversion reaction was carried out by the same procedure as in example 1 except that the contents of mercaptans and total mercaptan were changed to 11.78ppm, and the manganese oxide A2 prepared in preparation example 2 was used as an adsorbent.
Example 3
The adsorptive conversion reaction was carried out in the same manner as in example 1 except that n-hexane was selected as a solvent, propanethiol was selected as a material to be removed, and manganese oxide A3 prepared in production example 3 was used as an adsorbent.
Example 4
The adsorptive conversion reaction was carried out by the same procedure as in example 1 except that n-heptane was selected as a solvent, n-butylmercaptan was selected as a material to be removed, and manganese oxide A4 prepared in production example 4 was used as an adsorbent.
Example 5
The adsorptive conversion reaction was carried out by the same procedure as in example 1 except that isopentane was selected as a solvent, 3-methyl-1-butanethiol was selected as a material to be removed, and manganese oxide A5 prepared in preparation example 5 was used as an adsorbent.
Example 6
The adsorption conversion reaction was carried out by the same procedure as in example 1 except that n-octane was selected as a solvent, hexanethiol was selected as a material to be removed, and manganese oxide A6 obtained in preparation example 6 was used as an adsorbent.
Comparative example 1
The mercaptan-removal reaction was carried out in the same manner as in example 1, except that D1 was used as a desulfurizing agent in an amount of 0.4g by mass.
The specific surface area and pore volume of the oxides of manganese and the results of the sulfur concentration of the reaction products of examples 1 to 6 and comparative example 1 are shown in Table 1.
Table 1.
Figure BDA0003188826270000091
As can be seen from Table 1, the method of the present invention has significantly higher effect than the prior art when it is used for removing mercaptans from light naphtha, and has significant effect.
According to the physicochemical properties of the manganese oxide molecular sieve, the special crystal structure of the manganese oxide molecular sieve gives full play to the advantages of the manganese oxide molecular sieve in the field of liquefied gas desulfurization, so that the manganese oxide molecular sieve can have higher desulfurization depth than a comparative example at normal temperature and normal pressure. Meanwhile, the used manganese oxide molecular sieve has simple preparation method and good repeatability, and is beneficial to industrial popularization.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention can be made, and the same should be considered as the disclosure of the present invention as long as the idea of the present invention is not violated.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (10)

1. A process for removing thiol from light naphtha includes such steps as contacting the Mn oxide molecular sieve with the light naphtha containing thiol at ordinary temp-200 deg.C.
2. The method of claim 1, wherein the manganese oxide molecular sieve is selected from one or more of birnessite, manganesite, buchel, manganebite, birnessite, and calciumusite.
3. The method of claim 1, wherein the manganese oxide molecular sieve is prepared by: (1) Carrying out hydrothermal synthesis reaction on an aqueous solution containing an oxidized manganese compound and a reduced manganese compound; (2) And collecting a solid product, washing, drying and roasting to obtain the manganese oxide molecular sieve.
4. The method according to claim 3, wherein the temperature of the hydrothermal synthesis reaction is 60-200 ℃ and the reaction time is 1-36 h.
5. The method according to claim 3, wherein the oxidized manganese compound is selected from one or more of potassium permanganate, potassium manganate and sodium permanganate, and the reduced manganese compound is selected from one or more of manganese sulfate, manganese nitrate, manganese acetate and manganese chloride.
6. The method according to claim 3, wherein the molar ratio of the oxidized manganese compound to the reduced manganese compound is (0.2 to 3): 1.
7. the method of claim 3, wherein the drying temperature is 80-350 ℃ and the time is 1-24 h, and the roasting temperature is 200-900 ℃ and the time is 0.5-12 h.
8. The method according to claim 3, further comprising a step of adding an acid to the aqueous solution to adjust the pH of the aqueous solution to 0.2 to 3 before the hydrothermal synthesis reaction.
9. The method of claim 1, wherein the conditions of the contacting comprise: the pressure is normal pressure, the temperature is normal temperature to 150 ℃, and the volume space velocity is 0.1 to 100h -1 。
10. The method of claim 1, wherein the contacting is performed in a fixed bed reactor.
CN202110870183.2A 2021-07-30 2021-07-30 Method for removing mercaptan from light naphtha Pending CN115678591A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160175806A1 (en) * 2014-12-17 2016-06-23 University Of Connecticut Adsorptive desulfurization
CN112691651A (en) * 2020-12-22 2021-04-23 沈阳三聚凯特催化剂有限公司 Preparation method of desulfurizer, desulfurizer and application
CN112791721A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst precursor, supported catalyst, preparation method and activation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160175806A1 (en) * 2014-12-17 2016-06-23 University Of Connecticut Adsorptive desulfurization
CN112791721A (en) * 2019-10-28 2021-05-14 中国石油化工股份有限公司 Supported catalyst precursor, supported catalyst, preparation method and activation method
CN112691651A (en) * 2020-12-22 2021-04-23 沈阳三聚凯特催化剂有限公司 Preparation method of desulfurizer, desulfurizer and application

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